US11207645B2 - Composite semipermeable membrane and spiral wound separation membrane element - Google Patents
Composite semipermeable membrane and spiral wound separation membrane element Download PDFInfo
- Publication number
- US11207645B2 US11207645B2 US16/344,625 US201716344625A US11207645B2 US 11207645 B2 US11207645 B2 US 11207645B2 US 201716344625 A US201716344625 A US 201716344625A US 11207645 B2 US11207645 B2 US 11207645B2
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- US
- United States
- Prior art keywords
- segment
- mol
- polyamide
- based resin
- composite semipermeable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000012528 membrane Substances 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000000926 separation method Methods 0.000 title claims abstract description 9
- 150000001412 amines Chemical class 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 44
- 229920002647 polyamide Polymers 0.000 claims abstract description 41
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229940018564 m-phenylenediamine Drugs 0.000 claims abstract description 39
- -1 diamine compound Chemical class 0.000 claims abstract description 34
- 239000002253 acid Substances 0.000 claims abstract description 27
- 150000004820 halides Chemical class 0.000 claims abstract description 27
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 7
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 230000035699 permeability Effects 0.000 abstract description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 44
- 239000010410 layer Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 20
- 239000007864 aqueous solution Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 6
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 6
- 239000011247 coating layer Substances 0.000 description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 229940083575 sodium dodecyl sulfate Drugs 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 description 4
- LDQMZKBIBRAZEA-UHFFFAOYSA-N 2,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C(N)=C1 LDQMZKBIBRAZEA-UHFFFAOYSA-N 0.000 description 4
- QCESOQYTNNRNNY-UHFFFAOYSA-N 4-bromo-3,5-difluorobenzenesulfonyl chloride Chemical compound FC1=CC(S(Cl)(=O)=O)=CC(F)=C1Br QCESOQYTNNRNNY-UHFFFAOYSA-N 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920002492 poly(sulfone) Polymers 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009292 forward osmosis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FWJFNQHPFXHOAC-UHFFFAOYSA-N methyl 2,4-diaminobenzoate Chemical compound COC(=O)C1=CC=C(N)C=C1N FWJFNQHPFXHOAC-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- ZKVMMSGRDBQIOQ-UHFFFAOYSA-N 1,1,2-trichloro-1-fluoroethane Chemical compound FC(Cl)(Cl)CCl ZKVMMSGRDBQIOQ-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- UQBNGMRDYGPUOO-UHFFFAOYSA-N 1-n,3-n-dimethylbenzene-1,3-diamine Chemical compound CNC1=CC=CC(NC)=C1 UQBNGMRDYGPUOO-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical compound COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 description 1
- SKQKFNDHTJCKDQ-UHFFFAOYSA-N 2,4-bis(methylamino)benzoic acid Chemical compound CNC1=CC=C(C(O)=O)C(NC)=C1 SKQKFNDHTJCKDQ-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- ITTFEPALADGOBD-UHFFFAOYSA-N 2-butylpropanedioyl dichloride Chemical compound CCCCC(C(Cl)=O)C(Cl)=O ITTFEPALADGOBD-UHFFFAOYSA-N 0.000 description 1
- IPOVOSHRRIJKBR-UHFFFAOYSA-N 2-ethylpropanedioyl dichloride Chemical compound CCC(C(Cl)=O)C(Cl)=O IPOVOSHRRIJKBR-UHFFFAOYSA-N 0.000 description 1
- MLNSYGKGQFHSNI-UHFFFAOYSA-N 2-propylpropanedioyl dichloride Chemical compound CCCC(C(Cl)=O)C(Cl)=O MLNSYGKGQFHSNI-UHFFFAOYSA-N 0.000 description 1
- BWBUMOXWLPAYFU-UHFFFAOYSA-N 3,5-bis(methylamino)benzoic acid Chemical compound CNC1=CC(NC)=CC(C(O)=O)=C1 BWBUMOXWLPAYFU-UHFFFAOYSA-N 0.000 description 1
- TYJLAVGMVTXZQD-UHFFFAOYSA-N 3-chlorosulfonylbenzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(S(Cl)(=O)=O)=C1C(Cl)=O TYJLAVGMVTXZQD-UHFFFAOYSA-N 0.000 description 1
- GNIZQCLFRCBEGE-UHFFFAOYSA-N 3-phenylbenzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(Cl)=O GNIZQCLFRCBEGE-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- YARQLHBOIGUVQM-UHFFFAOYSA-N benzene-1,2,3-trisulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC(S(Cl)(=O)=O)=C1S(Cl)(=O)=O YARQLHBOIGUVQM-UHFFFAOYSA-N 0.000 description 1
- YBGQXNZTVFEKEN-UHFFFAOYSA-N benzene-1,2-disulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1S(Cl)(=O)=O YBGQXNZTVFEKEN-UHFFFAOYSA-N 0.000 description 1
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- BZFATHSFIGBGOT-UHFFFAOYSA-N butane-1,1,1-tricarbonyl chloride Chemical compound CCCC(C(Cl)=O)(C(Cl)=O)C(Cl)=O BZFATHSFIGBGOT-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XWALRFDLDRDCJG-UHFFFAOYSA-N cyclobutane-1,1,2,2-tetracarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCC1(C(Cl)=O)C(Cl)=O XWALRFDLDRDCJG-UHFFFAOYSA-N 0.000 description 1
- LXLCHRQXLFIZNP-UHFFFAOYSA-N cyclobutane-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCC1 LXLCHRQXLFIZNP-UHFFFAOYSA-N 0.000 description 1
- PBWUKDMYLKXAIP-UHFFFAOYSA-N cyclohexane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CCCCC1(C(Cl)=O)C(Cl)=O PBWUKDMYLKXAIP-UHFFFAOYSA-N 0.000 description 1
- MLCGVCXKDYTMRG-UHFFFAOYSA-N cyclohexane-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCCC1 MLCGVCXKDYTMRG-UHFFFAOYSA-N 0.000 description 1
- SSJXIUAHEKJCMH-UHFFFAOYSA-N cyclohexane-1,2-diamine Chemical compound NC1CCCCC1N SSJXIUAHEKJCMH-UHFFFAOYSA-N 0.000 description 1
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 1
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 description 1
- DCXMNNZFVFSGJX-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCC1(C(Cl)=O)C(Cl)=O DCXMNNZFVFSGJX-UHFFFAOYSA-N 0.000 description 1
- JREFGECMMPJUHM-UHFFFAOYSA-N cyclopentane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CCCC1(C(Cl)=O)C(Cl)=O JREFGECMMPJUHM-UHFFFAOYSA-N 0.000 description 1
- YYLFLXVROAGUFH-UHFFFAOYSA-N cyclopentane-1,1-dicarbonyl chloride Chemical compound ClC(=O)C1(C(Cl)=O)CCCC1 YYLFLXVROAGUFH-UHFFFAOYSA-N 0.000 description 1
- CRMQURWQJQPUMY-UHFFFAOYSA-N cyclopropane-1,1,2-tricarbonyl chloride Chemical compound ClC(=O)C1CC1(C(Cl)=O)C(Cl)=O CRMQURWQJQPUMY-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- QIRAYNIFEOXSPW-UHFFFAOYSA-N dimepheptanol Chemical compound C=1C=CC=CC=1C(CC(C)N(C)C)(C(O)CC)C1=CC=CC=C1 QIRAYNIFEOXSPW-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QTOWGAPJBGYFPH-UHFFFAOYSA-N methyl 2,4-bis(methylamino)benzoate Chemical compound COC(C1=C(C=C(C=C1)NC)NC)=O QTOWGAPJBGYFPH-UHFFFAOYSA-N 0.000 description 1
- KVBVAFAGNOGWPJ-UHFFFAOYSA-N methyl 3,5-bis(methylamino)benzoate Chemical compound CNC1=CC(NC)=CC(C(=O)OC)=C1 KVBVAFAGNOGWPJ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- OCIDXARMXNJACB-UHFFFAOYSA-N n'-phenylethane-1,2-diamine Chemical compound NCCNC1=CC=CC=C1 OCIDXARMXNJACB-UHFFFAOYSA-N 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- WUQGUKHJXFDUQF-UHFFFAOYSA-N naphthalene-1,2-dicarbonyl chloride Chemical compound C1=CC=CC2=C(C(Cl)=O)C(C(=O)Cl)=CC=C21 WUQGUKHJXFDUQF-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MEQCXWDKLOGGRO-UHFFFAOYSA-N oxolane-2,3,4,5-tetracarbonyl chloride Chemical compound ClC(=O)C1OC(C(Cl)=O)C(C(Cl)=O)C1C(Cl)=O MEQCXWDKLOGGRO-UHFFFAOYSA-N 0.000 description 1
- LSHSZIMRIAJWRM-UHFFFAOYSA-N oxolane-2,3-dicarbonyl chloride Chemical compound ClC(=O)C1CCOC1C(Cl)=O LSHSZIMRIAJWRM-UHFFFAOYSA-N 0.000 description 1
- MTAAPVANJNSBGV-UHFFFAOYSA-N pentane-1,1,1-tricarbonyl chloride Chemical compound CCCCC(C(Cl)=O)(C(Cl)=O)C(Cl)=O MTAAPVANJNSBGV-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- GHAIYFTVRRTBNG-UHFFFAOYSA-N piperazin-1-ylmethanamine Chemical compound NCN1CCNCC1 GHAIYFTVRRTBNG-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- VLRIRAGKJXODNO-UHFFFAOYSA-N propane-1,1,1-tricarbonyl chloride Chemical compound CCC(C(Cl)=O)(C(Cl)=O)C(Cl)=O VLRIRAGKJXODNO-UHFFFAOYSA-N 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N tris(2-aminoethyl)amine Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/10—Spiral-wound membrane modules
Definitions
- the present invention relates to a composite semipermeable membrane and a spiral wound separation membrane element.
- the composite semipermeable membrane and the spiral wound separation membrane element are suitably used for production of ultrapure water, desalination of brackish water or sea water, etc., and usable for removing or collecting pollution sources or effective substances from pollution, which causes environment pollution occurrence, such as dyeing drainage and electrodeposition paint drainage, leading to contribute to closed system for drainage.
- the membrane can be used for concentration of active ingredients in foodstuffs usage, for an advanced water treatment, such as removal of harmful component in water purification and sewage usage etc.
- the membrane can be used for waste water treatment in oil fields or shale gas fields.
- the composite semipermeable membrane is called an RO (reverse osmosis) membrane, an NF (nanofiltration) membrane, or a FO (forward osmosis) membrane, depending on the filtration performance and treatment method of the membrane, and such membrane can be used for the production of ultrapure water, seawater desalination, desalination of brackish water, waste water recycling treatment, or the like.
- Patent Document 1 a composite semipermeable membrane in which a thin layer containing a crosslinked polyamide obtained by polycondensation of a polyfunctional acid halide and a polyfunctional amine component is formed on a supporting film has been proposed.
- Patent Document 1 JP-A-2004-237230
- An object of the present invention is to provide a composite semipermeable membrane which has three excellent properties including ionic substance rejecting property, nonionic substance rejecting property, and water permeability in a well-balanced manner for practical use; and a spiral wound separation membrane element which comprises this composite semipermeable membrane.
- the inventors of the invention have made extensive studies to solve the above-mentioned problems, and, as a result, have found that the purpose can be achieved by the following composite semipermeable membrane and have completed the invention.
- the present invention relates to a composite semipermeable membrane having a skin layer containing a polyamide-based resin on a surface of a porous support, wherein the polyamide-based resin is obtained by polymerizing a polyfunctional acid halide component and a polyfunctional amine component, and the polyfunctional amine component contains m-phenylenediamine and at least one diamine compound represented by general formula (1) below:
- R 1 and R 2 represents COOH, and the other represents a hydrogen atom; and each of R 3 and R 4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and
- a ratio (mol %) of a segment (A) derived from m-phenylenediamine and a segment (B) derived from the diamine compound in the polyamide-based resin is 99.9:0.1 to 98:2 (segment (A):segment (B)).
- the present invention relates to a composite semipermeable membrane having a skin layer containing a polyamide-based resin on a surface of a porous support, wherein
- the polyamide-based resin is obtained by polymerizing a polyfunctional acid halide component and a polyfunctional amine component, and the polyfunctional amine component contains m-phenylenediamine and at least one diamine compound represented by general formula (2) below:
- R 5 and R 6 represents COOR 9 , and the other represents a hydrogen atom;
- R 9 represents an alkyl group having 1 to 4 carbon atoms, and each of R 7 and R 8 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and
- a ratio (mol %) of a segment (A) derived from m-phenylenediamine and a segment (C) derived from the diamine compound in the polyamide-based resin is 97:3 to 83:17 (segment (A):segment (C)).
- the inventors of the present invention have found that by forming a skin layer with use of a polyamide-based resin containing a segment (A) derived from m-phenylenediamine and a segment (B) derived from a diamine compound represented by the general formula (1) or a segment (C) derived from a diamine compound represented by the general formula (2) at a specific ratio, a composite semipermeable membrane which has three excellent properties including ionic substance rejecting property, nonionic substance rejecting property, and water permeability in a well-balanced manner for practical use can be obtained.
- the ratio (mol %) of the segment (B) derived from the diamine compound represented by the general formula (1) is less than 0.1, the water permeability of the composite semipermeable membrane becomes insufficient. The reason for this is considered to be due to a small content of a hydrophilic substituent in the polyamide-based resin.
- the ratio (mol %) of the segment (B) exceeds 2, the ionic substance and/or nonionic substance rejecting property of the composite semipermeable membrane decreases. The reason for this is considered to be that although the content of the hydrophilic substituent in the polyamide-based resin increases, a three-dimensional structure of the polyamide-based resin becomes coarse due to steric hindrance of the hydrophilic substituent.
- the ratio (mol %) of the segment (C) derived from the diamine compound represented by the general formula (2) is less than 3, the water permeability of the composite semipermeable membrane becomes insufficient for the same reason as above.
- the ratio (mol %) of the segment (C) exceeds 17, the ionic substance and/or nonionic substance rejecting property of the composite semipermeable membrane decreases for the same reason as above.
- a total amount of the segment (A) and the segment (B) is 50 mol % or more when an amount of a segment derived from all polyfunctional amine components is 100 mol % in the polyamide-based resin.
- the effect of the present invention is further improved.
- a total amount of the segment (A) and the segment (C) is 50 mol % or more when an amount of a segment derived from all the polyfunctional amine components is 100 mol % in the polyamide-based resin.
- the effect of the present invention is further improved.
- the total amount of the segment (A) and the segment (B) is 50 to 70 mol % when an amount of a segment derived from all monomer components is 100 mol % in the polyamide-based resin.
- the total amount of the segment (A) and the segment (B) is out of the above range, any or all of ionic substance rejecting property, nonionic substance rejecting property, and water permeability tend to decrease.
- the total amount of the segment (A) and the segment (C) is 50 to 70 mol % when an amount of a segment derived from all the monomer components is 100 mol % in the polyamide-based resin.
- the total amount of the segment (A) and the segment (C) is out of the above range, any or all of ionic substance rejecting property, nonionic substance rejecting property, and water permeability tend to decrease.
- the spiral wound separation membrane element of the present invention includes the composite semipermeable membrane as a constituent member thereof.
- the composite semipermeable membrane of the present invention has three excellent properties including ionic substance rejecting property, nonionic substance rejecting property, and water permeability in a well-balanced manner for practical use.
- Use of the composite semipermeable membrane of the present invention makes it possible to efficiently purify high purity water from raw water containing an ionic substance and a nonionic substance.
- a skin layer containing a polyamide-based resin is formed on a surface of a porous support.
- the skin layer is a layer that acts as a main functional layer in filtration.
- the polyamide-based resin is obtained by polymerizing at least a polyfunctional amine component and a polyfunctional acid halide component.
- the polyfunctional amine component at least m-phenylenediamine and a diamine compound represented by the following general formula (1) are used.
- R 1 and R 2 represents COOH, and the other represents a hydrogen atom; and each of R 3 and R 4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- R 3 and R 4 are each independently hydrogen or a methyl group.
- diamine compounds it is preferable to use at least one member selected from the group consisting of 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, N,N′-dimethyl-3,5-diaminobenzoic acid, and N,N′-dimethyl-2,4-diaminobenzoic acid. It is more preferable to use at least one member selected from the group consisting of 3,5-diaminobenzoic acid and 2,4-diaminobenzoic acid.
- the polyfunctional amine component at least m-phenylenediamine and the diamine compound represented by the following general formula (2) may be used.
- R 5 and R 6 represents COOR 9 , and the other represents a hydrogen atom;
- R 9 represents an alkyl group having 1 to 4 carbon atoms, and each of R 7 and R 8 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- R 9 is a methyl group, and that R 7 and R 8 are each independently hydrogen or a methyl group.
- the diamine compounds it is preferable to use at least one member selected from the group consisting of methyl 3,5-diaminobenzoate, methyl 2,4-diaminobenzoate, methyl N,N′-dimethyl-3,5-diaminobenzoate, and methyl N,N′-dimethyl-2,4-diaminobenzoate. It is more preferable to use at least one member selected from the group consisting of methyl 3,5-diaminobenzoate and methyl 2,4-diaminobenzoate.
- At least m-phenylenediamine, the diamine compound represented by the general formula (1), and the diamine compound represented by the general formula (2) may be used as the polyfunctional amine component.
- An aromatic, aliphatic or alicyclic polyfunctional amine other than m-phenylenediamine and the diamine compound may be used in combination as the polyfunctional amine component.
- the aromatic polyfunctional amines include, for example, p-phenylenediamine, o-phenylenediamine, 1,3,5-triamino benzene, 1,2,4-triamino benzene, 2,4-diaminotoluene, 2,6-diaminotoluene, N,N′-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidol, xylylene diamine etc.
- the aliphatic polyfunctional amines include, for example, ethylenediamine, propylenediamine, tris(2-aminoethyl)amine, n-phenylethylenediamine, etc.
- the alicyclic polyfunctional amines include, for example, 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, 4-aminomethyl piperazine, etc.
- polyfunctional amines may be used independently, and two or more kinds may be used in combination. In order to obtain a skin layer having a higher salt-rejecting property, it is preferred to use the aromatic polyfunctional amines.
- the polyfunctional acid halide component represents polyfunctional acid halides having two or more reactive carbonyl groups.
- the polyfunctional acid halides include aromatic, aliphatic, and alicyclic polyfunctional acid halides.
- the aromatic polyfunctional acid halides include, for example trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyl dicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzenetrisulfonic acid trichloride, benzenedisulfonic acid dichloride, chlorosulfonyl benzenedicarboxylic acid dichloride etc.
- the aliphatic polyfunctional acid halides include, for example, propanedicarboxylic acid dichloride, butane dicarboxylic acid dichloride, pentanedicarboxylic acid dichloride, propane tricarboxylic acid trichloride, butane tricarboxylic acid trichloride, pentane tricarboxylic acid trichloride, glutaryl halide, adipoyl halide etc.
- the alicyclic polyfunctional acid halides include, for example, cyclopropane tricarboxylic acid trichloride, cyclobutanetetracarboxylic acid tetrachloride, cyclopentane tricarboxylic acid trichloride, cyclopentanetetracarboxylic acid tetrachloride, cyclohexanetricarboxylic acid trichloride, tetrahydrofurantetracarboxylic acid tetrachloride, cyclopentanedicarboxylic acid dichloride, cyclobutanedicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride, tetrahydrofuran dicarboxylic acid dichloride, etc.
- polyfunctional acid halides may be used independently, and two or more kinds may be used in combination. In order to obtain a skin layer having higher salt-rejecting property, it is preferred to use aromatic polyfunctional acid halides. In addition, it is preferred to form a cross linked structure using polyfunctional acid halides having trivalency or more as at least a part of the polyfunctional acid halide components.
- polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylic acids etc., and polyhydric alcohols, such as sorbitol and glycerin, may be copolymerized.
- the porous support for supporting the skin layer is not especially limited as long as it has a function for supporting the skin layer, and usually ultrafiltration membrane having micro pores with an average pore size approximately 10 to 500 angstroms may preferably be used.
- Materials for formation of the porous support include various materials, for example, polyarylether sulfones, such as polysulfones and polyether sulfones; polyimides; polyvinylidene fluorides; etc., and polysulfones and polyarylether sulfones are especially preferably used from a viewpoint of chemical, mechanical, and thermal stability.
- the thickness of this porous support is usually approximately 25 to 125 ⁇ m, and preferably approximately 40 to 75 ⁇ m, but the thickness is not necessarily limited to them.
- the porous support may be reinforced with backing by cloths, nonwoven fabric, etc.
- Processes for forming the skin layer including the polyamide resin on the surface of the porous support is not in particular limited, and any publicly known methods may be used.
- the publicly known methods include an interfacial condensation method, a phase separation method, a thin film application method, etc.
- the interfacial condensation method is a method, wherein an amine aqueous solution containing a polyfunctional amine component, an organic solution containing a polyfunctional acid halide component are forced to contact together to form a skin layer by an interfacial polymerization, and then the obtained skin layer is laid on a porous support, and a method wherein a skin layer of a polyamide resin is directly formed on a porous support by the above-described interfacial polymerization on a porous support. Details, such as conditions of the interfacial condensation method, are described in Japanese Patent Application Laid-Open No. S58-24303, Japanese Patent Application Laid-Open No. H01-180208, and these known methods are suitably employable.
- a skin layer by an interfacial polymerization method including forming a coating layer of an aqueous solution containing a polyfunctional amine component on a porous support and bringing an organic solution containing a polyfunctional acid halide component into contact with the coating layer of the aqueous solution.
- the concentration of the polyfunctional amine component in the amine aqueous solution is not in particular limited, the concentration is preferably 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight. Less than 0.1% by weight of the concentration of the polyfunctional amine component may easily cause defect such as pinhole in the skin layer, leading to tendency of deterioration of salt-rejecting property. On the other hand, the concentration of the polyfunctional amine component exceeding 10% by weight allows easy permeation of the polyfunctional amine component into the porous support to be an excessively large thickness and to raise the permeation resistance, likely giving deterioration of the permeation flux.
- an alcohol is preferably used in combination from the viewpoint that the alcohol makes the diamine compound represented by the general formula (1) or (2) dissolve easily to improve the reactivity of the diamine compound, so that the content of the segment (B) or the segment (C) derived from the diamine compound in the polyamide-based resin is increased.
- the alcohol to be used include methanol, ethanol, isopropyl alcohol and the like. These may be used alone, or two or more of them may be used in combination.
- the alcohol is preferably used in an amount of 0.1 to 50% by weight, more preferably 1 to 10% by weight, in the total solvent.
- the concentration of the polyfunctional acid halide component in the organic solution is not in particular limited, it is preferably 0.01 to 5% by weight, and more preferably 0.05 to 1% by weight. Less than 0.01% by weight of the concentration of the polyfunctional acid halide component is apt to make the unreacted polyfunctional amine component remain, to cause defect such as pinhole in the skin layer, leading to tendency of deterioration of salt-rejecting property. On the other hand, the concentration exceeding 5% by weight of the polyfunctional acid halide component is apt to make the unreacted polyfunctional acid halide component remain, to be an excessively large thickness and to raise the permeation resistance, likely giving deterioration of the permeation flux.
- the organic solvents used for the organic solution is not especially limited as long as they have small solubility to water, and do not cause degradation of the porous support, and dissolve the polyfunctional acid halide component.
- the solvents include saturated hydrocarbons, such as cyclohexane, heptane, octane, and nonane, halogenated hydrocarbons, such as 1,1,2-trichlorofluoroethane, etc.
- a saturated hydrocarbon or a naphthenic solvent which has a boiling point of preferably 300° C. or less, more preferably 200° C. or less, is used as the solvent for the organic solution.
- the organic solvent may be used singly or as a mixed solvent of two or more kinds thereof.
- additives may be added to the amine aqueous solution or the organic solution in order to provide easy film production and to improve performance of the composite semipermeable membrane to be obtained.
- the additives include, for example, surfactants, such as sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium lauryl sulfate; basic compounds, such as sodium hydroxide, trisodium phosphate, triethylamine, etc. for removing hydrogen halides formed by polymerization; acylation catalysts; compounds having a solubility parameter of 8 to 14 (cal/cm 2 ) 1/2 described in Japanese Patent Application Laid-Open No. H08-224452.
- the formed film on the porous support is heated to 20° C. or more to form a skin layer.
- the heating temperature is more preferably 20 to 200° C., even more preferably 100 to 150° C., particularly preferably 130 to 150° C.
- the polyamide-based resin used in the present invention which is a material for forming a skin layer, has a ratio (mol %) of the segment (A) derived from m-phenylenediamine and the segment (B) derived from the diamine compound in the resin of 99.9:0.1 to 98:2 (segment (A):segment (B)), preferably 99.8:0.2 to 98.2:1.8, more preferably 99.75:0.25 to 98.5:1.5, even more preferably 99.7:0.3 to 98.8:1.2, particularly preferably 99.65:0.35 to 98.9:1.1.
- the polyamide-based resin used in the present invention which is a material for forming a skin layer, has a ratio (mol %) of the segment (A) derived from m-phenylenediamine and the segment (C) derived from the diamine compound in the resin of 97:3 to 87:17 (segment (A):segment (C)).
- the total amount of the segment (A) and the segment (B) is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 90 mol % or more, when the amount of the segment derived from all the polyfunctional amine components is 100 mol %.
- the total amount of the segment (A) and the segment (C) is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 90 mol % or more, when the amount of the segment derived from all the polyfunctional amine components is 100 mol %.
- the total amount of the segment (A) and the segment (B) is preferably 50 to 70 mol %, more preferably from 55 to 65 mol %, even more preferably 56 to 63 mol %, particularly preferably 56 to 60 mol %, when the amount of the segment derived from all the monomer components in the resin is 100 mol %.
- segments other than the segment (A) and the segment (B) include segments derived from a polyfunctional amine other than m-phenylenediamine and the diamine compound, and segments derived from a polyfunctional acid halide.
- the total amount of the segment (A) and the segment (C) is preferably 50 to 70 mol % when the amount of the segment derived from all the monomer components in the resin is 100 mol %.
- segments other than the segment (A) and the segment (C) include segments derived from a polyfunctional amine other than m-phenylenediamine and the diamine compound, and segments derived from a polyfunctional acid halide.
- the thickness of the skin layer formed on the porous support is not in particular limited, and it is usually approximately 0.05 to 2 ⁇ m, and preferably 0.1 to 1 ⁇ m.
- the composite semipermeable membrane of the present invention there is no limitation on the shape of the composite semipermeable membrane of the present invention. That is, the composite semipermeable membrane can take any conceivable membrane shapes, such as a flat membrane or a spiral element. Further, conventionally known various treatments may be applied to the composite semipermeable membrane so as to improve its salt-rejecting property, water permeability, and oxidation resistance.
- the spiral wound separation membrane element of the present invention can be produced by a known method using the composite semipermeable membrane.
- a prepared flat shape composite semipermeable membrane was cut into a predetermined shape and size and was set in a flat membrane evaluation cell.
- An aqueous solution containing 3.2% by weight of sodium chloride and 5 ppm of boron (boric acid 29 ppm) and being adjusted to pH 6.5 to 7 using NaOH was brought into contact with the membrane at 25° C. by applying a differential pressure of 5.5 MPa to the feed side and the permeation side of the membrane for 1 hour, and then the sodium chloride rejecting rate, boron rejecting rate, and permeation flux were measured.
- sodium chloride rejecting rate an ordinary electric conductivity was measurement, and as for the boron rejecting rate, a concentration was measured by an ICP analyzer. From the measurement results above, calculation was performed according to the following equations.
- a prepared flat shape composite semipermeable membrane was cut into a predetermined shape and size and was set in a flat membrane evaluation cell. Then, an aqueous solution of isopropyl alcohol (IPA) with a concentration of 0.15% by weight was permeated through the composite semipermeable membrane for 30 minutes at an operation pressure of 1.5 MPa, a temperature of 25° C. and a pH of 6.5, and then the IPA rejecting rate was measured. As for the IPA rejecting rate, each IPA concentration in the supply solution and the permeation solution was measured by GC analyzer. From the measurement results above, calculation was performed according to the following equation.
- IPA isopropyl alcohol
- ⁇ IPA Rejecting Rate> Rejecting rate (%) (1 ⁇ (IPA concentration in membrane-permeation solution/IPA concentration in supply solution)) ⁇ 100 (Measurement of Amount of Each Segment in Polyamide-Based Resin)
- a prepared composite semipermeable membrane was immersed in cyclohexanone, and the polyamide-based resin of the skin layer was recovered and collected in a stainless-steel tube. After addition of methanol and alkali thereto, the mixture was heated at 240° C. for 1 hour to decompose the polyamide-based resin.
- the content ratio of MPD and DABA in the amine aqueous solution is about 80 mol % MPD and about 20 mol % DABA.
- a surface of the aqueous coating layer was immersed in an acid chloride solution containing 0.075% by weight of trimesic acid chloride (TMC) and 0.113% by weight of isophthalic acid chloride (IPC) dissolved in a naphthenic solvent (Exxsol D40, manufactured by Exxon Mobil Corporation) for 7 seconds. Thereafter, an excess solution on the surface of the aqueous coating layer was removed, and the coating layer was air-dried for 20 seconds and further kept in a hot air dryer at 140° C. for 3 minutes to form a skin layer containing a polyamide-based resin on the porous polysulfone support, thereby forming a composite semipermeable membrane.
- TMC trimesic acid chloride
- IPC isophthalic acid chloride
- a composite semipermeable membrane was prepared in the same manner as in Example 1, except that an amine aqueous solution containing 2.1% by weight of m-phenylenediamine (MPD), 1.3% by weight of 3,5-diaminobenzoic acid (DABA), 0.15% by weight of sodium dodecylsulfate, 2.15% by weight of triethylamine, 0.31% by weight of sodium hydroxide, 6% by weight of camphorsulfonic acid, and 1% by weight of isopropyl alcohol was used.
- the content ratio of MPD and DABA in the amine aqueous solution is about 70 mol % MPD and about 30 mol % DABA.
- a composite semipermeable membrane was prepared in the same manner as in Example 1, except that an amine aqueous solution containing 1.5% by weight of m-phenylenediamine (MPD), 2.1% by weight of 3,5-diaminobenzoic acid (DABA), 0.15% by weight of sodium dodecylsulfate, 2.15% by weight of triethylamine, 0.31% by weight of sodium hydroxide, 6% by weight of camphorsulfonic acid, and 1% by weight of isopropyl alcohol was used.
- the content ratio of MPD and DABA in the amine aqueous solution is about 50 mol % MPD and about 50 mol % DABA.
- a composite semipermeable membrane was prepared in the same manner as in Example 1, except that an amine aqueous solution containing 2.7% by weight of m-phenylenediamine (MPD), 0.45% by weight of methyl 3,5-diaminobenzoate (DABAME), 0.15% by weight of sodium dodecylsulfate, 2.15% by weight of triethylamine, 0.31% by weight of sodium hydroxide, 6% by weight of camphorsulfonic acid, and 1% by weight of isopropyl alcohol was used.
- the content ratio of MPD and DABAME in the amine aqueous solution is about 90 mol % MPD and about 10 mol % DABAME.
- a composite semipermeable membrane was prepared in the same manner as in Example 1 except that the formulation was changed to those as shown in Table 1.
- the composite semipermeable membrane and the spiral wound separation membrane element of the present invention are suitably used for production of ultrapure water, desalination of brackish water or sea water, etc., and usable for removing or collecting pollution sources or effective substances from pollution, which causes environment pollution occurrence, such as dyeing drainage and electrodeposition paint drainage, leading to contribute to closed system for drainage.
- the membrane can be used for concentration of active ingredients in foodstuffs usage, for an advanced water treatment, such as removal of harmful component in water purification and sewage usage etc.
- the membrane can be used for waste water treatment in oil fields or shale gas fields.
Abstract
The purpose of the present invention is to provide: a composite semipermeable membrane which has three excellent properties, namely, excellent ionic substance rejecting property, excellent nonionic substance rejecting property and excellent water permeability in a practically balanced manner, and a spiral wound separation membrane element which comprises this composite semipermeable membrane. A composite semipermeable membrane according to the present invention is obtained by forming a skin layer that contains a polyamide-based resin on a surface of a porous support, and is configured such that: the polyamide-based resin is obtained by polymerizing a polyfunctional acid halide component and a polyfunctional amine component; the polyfunctional amine component contains m-phenylenediamine and at least one diamine compound represented by general formula (1); and a ratio (mol %) of a segment (A) derived from m-phenylenediamine and a segment (B) derived from the diamine compound in the polyamide-based resin is 99.9:0.1 to 98:2 (segment (A):segment (B)).
Description
This application is a 371 of PCT/JP2017/038486, filed Oct. 25, 2017.
The present invention relates to a composite semipermeable membrane and a spiral wound separation membrane element. The composite semipermeable membrane and the spiral wound separation membrane element are suitably used for production of ultrapure water, desalination of brackish water or sea water, etc., and usable for removing or collecting pollution sources or effective substances from pollution, which causes environment pollution occurrence, such as dyeing drainage and electrodeposition paint drainage, leading to contribute to closed system for drainage. Furthermore, the membrane can be used for concentration of active ingredients in foodstuffs usage, for an advanced water treatment, such as removal of harmful component in water purification and sewage usage etc. Moreover, the membrane can be used for waste water treatment in oil fields or shale gas fields.
The composite semipermeable membrane is called an RO (reverse osmosis) membrane, an NF (nanofiltration) membrane, or a FO (forward osmosis) membrane, depending on the filtration performance and treatment method of the membrane, and such membrane can be used for the production of ultrapure water, seawater desalination, desalination of brackish water, waste water recycling treatment, or the like.
As a composite semipermeable membrane used industrially, for example, a composite semipermeable membrane in which a thin layer containing a crosslinked polyamide obtained by polycondensation of a polyfunctional acid halide and a polyfunctional amine component is formed on a supporting film has been proposed (Patent Document 1).
Patent Document 1: JP-A-2004-237230
Conventional composite semipermeable membranes have had insufficient water permeability. There has been a trade-off problem such that when water permeability is improved, a rejecting property of ionic substances and/or nonionic substances is deteriorated.
An object of the present invention is to provide a composite semipermeable membrane which has three excellent properties including ionic substance rejecting property, nonionic substance rejecting property, and water permeability in a well-balanced manner for practical use; and a spiral wound separation membrane element which comprises this composite semipermeable membrane.
The inventors of the invention have made extensive studies to solve the above-mentioned problems, and, as a result, have found that the purpose can be achieved by the following composite semipermeable membrane and have completed the invention.
That is, the present invention relates to a composite semipermeable membrane having a skin layer containing a polyamide-based resin on a surface of a porous support, wherein the polyamide-based resin is obtained by polymerizing a polyfunctional acid halide component and a polyfunctional amine component, and the polyfunctional amine component contains m-phenylenediamine and at least one diamine compound represented by general formula (1) below:
wherein one of R1 and R2 represents COOH, and the other represents a hydrogen atom; and each of R3 and R4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and
a ratio (mol %) of a segment (A) derived from m-phenylenediamine and a segment (B) derived from the diamine compound in the polyamide-based resin is 99.9:0.1 to 98:2 (segment (A):segment (B)).
Also, the present invention relates to a composite semipermeable membrane having a skin layer containing a polyamide-based resin on a surface of a porous support, wherein
the polyamide-based resin is obtained by polymerizing a polyfunctional acid halide component and a polyfunctional amine component, and the polyfunctional amine component contains m-phenylenediamine and at least one diamine compound represented by general formula (2) below:
wherein one of R5 and R6 represents COOR9, and the other represents a hydrogen atom; R9 represents an alkyl group having 1 to 4 carbon atoms, and each of R7 and R8 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and
a ratio (mol %) of a segment (A) derived from m-phenylenediamine and a segment (C) derived from the diamine compound in the polyamide-based resin is 97:3 to 83:17 (segment (A):segment (C)).
The inventors of the present invention have found that by forming a skin layer with use of a polyamide-based resin containing a segment (A) derived from m-phenylenediamine and a segment (B) derived from a diamine compound represented by the general formula (1) or a segment (C) derived from a diamine compound represented by the general formula (2) at a specific ratio, a composite semipermeable membrane which has three excellent properties including ionic substance rejecting property, nonionic substance rejecting property, and water permeability in a well-balanced manner for practical use can be obtained. Although the reason why such an effect can be obtained is not clear, it is known that, in general, when a highly reactive monomer is used, the crosslinking density of a skin layer tends to decrease, but the diamine compound represented by the general formula (1) or (2) has low reactivity as compared with m-phenylenediamine and additionally has a hydrophilic substituent. Thus, the reason why such an effect can be obtained is considered to be due to improvement in hydrophilicity of the skin layer without lowering crosslinking density of the skin layer.
When the ratio (mol %) of the segment (B) derived from the diamine compound represented by the general formula (1) is less than 0.1, the water permeability of the composite semipermeable membrane becomes insufficient. The reason for this is considered to be due to a small content of a hydrophilic substituent in the polyamide-based resin. On the other hand, when the ratio (mol %) of the segment (B) exceeds 2, the ionic substance and/or nonionic substance rejecting property of the composite semipermeable membrane decreases. The reason for this is considered to be that although the content of the hydrophilic substituent in the polyamide-based resin increases, a three-dimensional structure of the polyamide-based resin becomes coarse due to steric hindrance of the hydrophilic substituent.
Further, when the ratio (mol %) of the segment (C) derived from the diamine compound represented by the general formula (2) is less than 3, the water permeability of the composite semipermeable membrane becomes insufficient for the same reason as above. On the other hand, when the ratio (mol %) of the segment (C) exceeds 17, the ionic substance and/or nonionic substance rejecting property of the composite semipermeable membrane decreases for the same reason as above.
It is preferable that a total amount of the segment (A) and the segment (B) is 50 mol % or more when an amount of a segment derived from all polyfunctional amine components is 100 mol % in the polyamide-based resin. When the total amount of the segment (A) and the segment (B) is 50 mol % or more, the effect of the present invention is further improved.
It is preferable that a total amount of the segment (A) and the segment (C) is 50 mol % or more when an amount of a segment derived from all the polyfunctional amine components is 100 mol % in the polyamide-based resin. When the total amount of the segment (A) and the segment (C) is 50 mol % or more, the effect of the present invention is further improved.
It is preferable that the total amount of the segment (A) and the segment (B) is 50 to 70 mol % when an amount of a segment derived from all monomer components is 100 mol % in the polyamide-based resin. When the total amount of the segment (A) and the segment (B) is out of the above range, any or all of ionic substance rejecting property, nonionic substance rejecting property, and water permeability tend to decrease.
It is preferable that the total amount of the segment (A) and the segment (C) is 50 to 70 mol % when an amount of a segment derived from all the monomer components is 100 mol % in the polyamide-based resin. When the total amount of the segment (A) and the segment (C) is out of the above range, any or all of ionic substance rejecting property, nonionic substance rejecting property, and water permeability tend to decrease.
The spiral wound separation membrane element of the present invention includes the composite semipermeable membrane as a constituent member thereof.
The composite semipermeable membrane of the present invention has three excellent properties including ionic substance rejecting property, nonionic substance rejecting property, and water permeability in a well-balanced manner for practical use. Use of the composite semipermeable membrane of the present invention makes it possible to efficiently purify high purity water from raw water containing an ionic substance and a nonionic substance.
The embodiments of the invention will be described below.
In the composite semipermeable membrane of the present invention, a skin layer containing a polyamide-based resin is formed on a surface of a porous support. The skin layer is a layer that acts as a main functional layer in filtration.
The polyamide-based resin is obtained by polymerizing at least a polyfunctional amine component and a polyfunctional acid halide component.
In the present invention, as the polyfunctional amine component, at least m-phenylenediamine and a diamine compound represented by the following general formula (1) are used.
(In the formula (1), one of R1 and R2 represents COOH, and the other represents a hydrogen atom; and each of R3 and R4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
It is preferred that R3 and R4 are each independently hydrogen or a methyl group.
Among the diamine compounds, it is preferable to use at least one member selected from the group consisting of 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, N,N′-dimethyl-3,5-diaminobenzoic acid, and N,N′-dimethyl-2,4-diaminobenzoic acid. It is more preferable to use at least one member selected from the group consisting of 3,5-diaminobenzoic acid and 2,4-diaminobenzoic acid.
In the present invention, as the polyfunctional amine component, at least m-phenylenediamine and the diamine compound represented by the following general formula (2) may be used.
(In the formula (2), one of R5 and R6 represents COOR9, and the other represents a hydrogen atom; R9 represents an alkyl group having 1 to 4 carbon atoms, and each of R7 and R8 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)
It is preferred that R9 is a methyl group, and that R7 and R8 are each independently hydrogen or a methyl group.
Among the diamine compounds, it is preferable to use at least one member selected from the group consisting of methyl 3,5-diaminobenzoate, methyl 2,4-diaminobenzoate, methyl N,N′-dimethyl-3,5-diaminobenzoate, and methyl N,N′-dimethyl-2,4-diaminobenzoate. It is more preferable to use at least one member selected from the group consisting of methyl 3,5-diaminobenzoate and methyl 2,4-diaminobenzoate.
Further, in the present invention, at least m-phenylenediamine, the diamine compound represented by the general formula (1), and the diamine compound represented by the general formula (2) may be used as the polyfunctional amine component.
An aromatic, aliphatic or alicyclic polyfunctional amine other than m-phenylenediamine and the diamine compound may be used in combination as the polyfunctional amine component.
The aromatic polyfunctional amines include, for example, p-phenylenediamine, o-phenylenediamine, 1,3,5-triamino benzene, 1,2,4-triamino benzene, 2,4-diaminotoluene, 2,6-diaminotoluene, N,N′-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidol, xylylene diamine etc.
The aliphatic polyfunctional amines include, for example, ethylenediamine, propylenediamine, tris(2-aminoethyl)amine, n-phenylethylenediamine, etc.
The alicyclic polyfunctional amines include, for example, 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, 4-aminomethyl piperazine, etc.
These polyfunctional amines may be used independently, and two or more kinds may be used in combination. In order to obtain a skin layer having a higher salt-rejecting property, it is preferred to use the aromatic polyfunctional amines.
The polyfunctional acid halide component represents polyfunctional acid halides having two or more reactive carbonyl groups.
The polyfunctional acid halides include aromatic, aliphatic, and alicyclic polyfunctional acid halides.
The aromatic polyfunctional acid halides include, for example trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyl dicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzenetrisulfonic acid trichloride, benzenedisulfonic acid dichloride, chlorosulfonyl benzenedicarboxylic acid dichloride etc.
The aliphatic polyfunctional acid halides include, for example, propanedicarboxylic acid dichloride, butane dicarboxylic acid dichloride, pentanedicarboxylic acid dichloride, propane tricarboxylic acid trichloride, butane tricarboxylic acid trichloride, pentane tricarboxylic acid trichloride, glutaryl halide, adipoyl halide etc.
The alicyclic polyfunctional acid halides include, for example, cyclopropane tricarboxylic acid trichloride, cyclobutanetetracarboxylic acid tetrachloride, cyclopentane tricarboxylic acid trichloride, cyclopentanetetracarboxylic acid tetrachloride, cyclohexanetricarboxylic acid trichloride, tetrahydrofurantetracarboxylic acid tetrachloride, cyclopentanedicarboxylic acid dichloride, cyclobutanedicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride, tetrahydrofuran dicarboxylic acid dichloride, etc.
These polyfunctional acid halides may be used independently, and two or more kinds may be used in combination. In order to obtain a skin layer having higher salt-rejecting property, it is preferred to use aromatic polyfunctional acid halides. In addition, it is preferred to form a cross linked structure using polyfunctional acid halides having trivalency or more as at least a part of the polyfunctional acid halide components.
Furthermore, in order to improve performance of the skin layer including the polyamide resin, polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylic acids etc., and polyhydric alcohols, such as sorbitol and glycerin, may be copolymerized.
The porous support for supporting the skin layer is not especially limited as long as it has a function for supporting the skin layer, and usually ultrafiltration membrane having micro pores with an average pore size approximately 10 to 500 angstroms may preferably be used. Materials for formation of the porous support include various materials, for example, polyarylether sulfones, such as polysulfones and polyether sulfones; polyimides; polyvinylidene fluorides; etc., and polysulfones and polyarylether sulfones are especially preferably used from a viewpoint of chemical, mechanical, and thermal stability. The thickness of this porous support is usually approximately 25 to 125 μm, and preferably approximately 40 to 75 μm, but the thickness is not necessarily limited to them. The porous support may be reinforced with backing by cloths, nonwoven fabric, etc.
Processes for forming the skin layer including the polyamide resin on the surface of the porous support is not in particular limited, and any publicly known methods may be used. For example, the publicly known methods include an interfacial condensation method, a phase separation method, a thin film application method, etc. The interfacial condensation method is a method, wherein an amine aqueous solution containing a polyfunctional amine component, an organic solution containing a polyfunctional acid halide component are forced to contact together to form a skin layer by an interfacial polymerization, and then the obtained skin layer is laid on a porous support, and a method wherein a skin layer of a polyamide resin is directly formed on a porous support by the above-described interfacial polymerization on a porous support. Details, such as conditions of the interfacial condensation method, are described in Japanese Patent Application Laid-Open No. S58-24303, Japanese Patent Application Laid-Open No. H01-180208, and these known methods are suitably employable.
In the present invention, it is preferred to form a skin layer by an interfacial polymerization method including forming a coating layer of an aqueous solution containing a polyfunctional amine component on a porous support and bringing an organic solution containing a polyfunctional acid halide component into contact with the coating layer of the aqueous solution.
In the interfacial polymerization method, although the concentration of the polyfunctional amine component in the amine aqueous solution is not in particular limited, the concentration is preferably 0.1 to 10% by weight, and more preferably 0.5 to 5% by weight. Less than 0.1% by weight of the concentration of the polyfunctional amine component may easily cause defect such as pinhole in the skin layer, leading to tendency of deterioration of salt-rejecting property. On the other hand, the concentration of the polyfunctional amine component exceeding 10% by weight allows easy permeation of the polyfunctional amine component into the porous support to be an excessively large thickness and to raise the permeation resistance, likely giving deterioration of the permeation flux.
Although water is mainly used as the solvent for the amine aqueous solution, an alcohol is preferably used in combination from the viewpoint that the alcohol makes the diamine compound represented by the general formula (1) or (2) dissolve easily to improve the reactivity of the diamine compound, so that the content of the segment (B) or the segment (C) derived from the diamine compound in the polyamide-based resin is increased. Examples of the alcohol to be used include methanol, ethanol, isopropyl alcohol and the like. These may be used alone, or two or more of them may be used in combination. The alcohol is preferably used in an amount of 0.1 to 50% by weight, more preferably 1 to 10% by weight, in the total solvent.
Although the concentration of the polyfunctional acid halide component in the organic solution is not in particular limited, it is preferably 0.01 to 5% by weight, and more preferably 0.05 to 1% by weight. Less than 0.01% by weight of the concentration of the polyfunctional acid halide component is apt to make the unreacted polyfunctional amine component remain, to cause defect such as pinhole in the skin layer, leading to tendency of deterioration of salt-rejecting property. On the other hand, the concentration exceeding 5% by weight of the polyfunctional acid halide component is apt to make the unreacted polyfunctional acid halide component remain, to be an excessively large thickness and to raise the permeation resistance, likely giving deterioration of the permeation flux.
The organic solvents used for the organic solution is not especially limited as long as they have small solubility to water, and do not cause degradation of the porous support, and dissolve the polyfunctional acid halide component. For example, the solvents include saturated hydrocarbons, such as cyclohexane, heptane, octane, and nonane, halogenated hydrocarbons, such as 1,1,2-trichlorofluoroethane, etc. A saturated hydrocarbon or a naphthenic solvent, which has a boiling point of preferably 300° C. or less, more preferably 200° C. or less, is used as the solvent for the organic solution. The organic solvent may be used singly or as a mixed solvent of two or more kinds thereof.
Various kinds of additives may be added to the amine aqueous solution or the organic solution in order to provide easy film production and to improve performance of the composite semipermeable membrane to be obtained. The additives include, for example, surfactants, such as sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium lauryl sulfate; basic compounds, such as sodium hydroxide, trisodium phosphate, triethylamine, etc. for removing hydrogen halides formed by polymerization; acylation catalysts; compounds having a solubility parameter of 8 to 14 (cal/cm2)1/2 described in Japanese Patent Application Laid-Open No. H08-224452.
In the present invention, it is preferable that after the amine aqueous solution is in contact with the organic solution, an excessive organic solution on the porous support is removed, and the formed film on the porous support is heated to 20° C. or more to form a skin layer. By heating the formed film, it is possible to improve the reactivity of the diamine compound represented by the general formula (1) or (2) to increase the content of the segment (B) or the segment (C) derived from the diamine compound in the polyamide-based resin. The heating temperature is more preferably 20 to 200° C., even more preferably 100 to 150° C., particularly preferably 130 to 150° C.
The polyamide-based resin used in the present invention, which is a material for forming a skin layer, has a ratio (mol %) of the segment (A) derived from m-phenylenediamine and the segment (B) derived from the diamine compound in the resin of 99.9:0.1 to 98:2 (segment (A):segment (B)), preferably 99.8:0.2 to 98.2:1.8, more preferably 99.75:0.25 to 98.5:1.5, even more preferably 99.7:0.3 to 98.8:1.2, particularly preferably 99.65:0.35 to 98.9:1.1.
The polyamide-based resin used in the present invention, which is a material for forming a skin layer, has a ratio (mol %) of the segment (A) derived from m-phenylenediamine and the segment (C) derived from the diamine compound in the resin of 97:3 to 87:17 (segment (A):segment (C)).
In the polyamide-based resin used in the present invention, the total amount of the segment (A) and the segment (B) is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 90 mol % or more, when the amount of the segment derived from all the polyfunctional amine components is 100 mol %.
In the polyamide-based resin used in the present invention, the total amount of the segment (A) and the segment (C) is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 90 mol % or more, when the amount of the segment derived from all the polyfunctional amine components is 100 mol %.
In the polyamide-based resin used in the present invention, the total amount of the segment (A) and the segment (B) is preferably 50 to 70 mol %, more preferably from 55 to 65 mol %, even more preferably 56 to 63 mol %, particularly preferably 56 to 60 mol %, when the amount of the segment derived from all the monomer components in the resin is 100 mol %. Examples of segments other than the segment (A) and the segment (B) include segments derived from a polyfunctional amine other than m-phenylenediamine and the diamine compound, and segments derived from a polyfunctional acid halide.
In the polyamide-based resin used in the present invention, the total amount of the segment (A) and the segment (C) is preferably 50 to 70 mol % when the amount of the segment derived from all the monomer components in the resin is 100 mol %. Examples of segments other than the segment (A) and the segment (C) include segments derived from a polyfunctional amine other than m-phenylenediamine and the diamine compound, and segments derived from a polyfunctional acid halide.
The thickness of the skin layer formed on the porous support is not in particular limited, and it is usually approximately 0.05 to 2 μm, and preferably 0.1 to 1 μm.
There is no limitation on the shape of the composite semipermeable membrane of the present invention. That is, the composite semipermeable membrane can take any conceivable membrane shapes, such as a flat membrane or a spiral element. Further, conventionally known various treatments may be applied to the composite semipermeable membrane so as to improve its salt-rejecting property, water permeability, and oxidation resistance.
The spiral wound separation membrane element of the present invention can be produced by a known method using the composite semipermeable membrane.
The present invention will, hereinafter, be described with reference to Examples, but the present invention is not limited at all by these Examples.
[Evaluation and Measurement Method]
(Measurement of Permeation Flux, Sodium Chloride Rejecting Rate, and Boron Rejecting Rate)
A prepared flat shape composite semipermeable membrane was cut into a predetermined shape and size and was set in a flat membrane evaluation cell. An aqueous solution containing 3.2% by weight of sodium chloride and 5 ppm of boron (boric acid 29 ppm) and being adjusted to pH 6.5 to 7 using NaOH was brought into contact with the membrane at 25° C. by applying a differential pressure of 5.5 MPa to the feed side and the permeation side of the membrane for 1 hour, and then the sodium chloride rejecting rate, boron rejecting rate, and permeation flux were measured. As for the sodium chloride rejecting rate, an ordinary electric conductivity was measurement, and as for the boron rejecting rate, a concentration was measured by an ICP analyzer. From the measurement results above, calculation was performed according to the following equations.
<Sodium Chloride Rejecting Rate>
Rejecting Rate (%)=(1−(Sodium chloride concentration in membrane-permeation solution/sodium chloride concentration in Supply Solution))×100
<Boron Rejecting Rate>
Rejecting rate (%)=(1−(Boron concentration in membrane-permeation solution/Boron concentration in supply solution))×100
(Measurement of IPA Rejecting Rate)
Rejecting Rate (%)=(1−(Sodium chloride concentration in membrane-permeation solution/sodium chloride concentration in Supply Solution))×100
<Boron Rejecting Rate>
Rejecting rate (%)=(1−(Boron concentration in membrane-permeation solution/Boron concentration in supply solution))×100
(Measurement of IPA Rejecting Rate)
A prepared flat shape composite semipermeable membrane was cut into a predetermined shape and size and was set in a flat membrane evaluation cell. Then, an aqueous solution of isopropyl alcohol (IPA) with a concentration of 0.15% by weight was permeated through the composite semipermeable membrane for 30 minutes at an operation pressure of 1.5 MPa, a temperature of 25° C. and a pH of 6.5, and then the IPA rejecting rate was measured. As for the IPA rejecting rate, each IPA concentration in the supply solution and the permeation solution was measured by GC analyzer. From the measurement results above, calculation was performed according to the following equation.
<IPA Rejecting Rate>
Rejecting rate (%)=(1−(IPA concentration in membrane-permeation solution/IPA concentration in supply solution))×100
(Measurement of Amount of Each Segment in Polyamide-Based Resin)
Rejecting rate (%)=(1−(IPA concentration in membrane-permeation solution/IPA concentration in supply solution))×100
(Measurement of Amount of Each Segment in Polyamide-Based Resin)
A prepared composite semipermeable membrane was immersed in cyclohexanone, and the polyamide-based resin of the skin layer was recovered and collected in a stainless-steel tube. After addition of methanol and alkali thereto, the mixture was heated at 240° C. for 1 hour to decompose the polyamide-based resin. After cooling to room temperature, the decomposed solution was collected and analyzed by 1H-NMR measurement (measuring apparatus: BRUKER Biospin, AVANCE III-600, measuring solvent: DMSO-d6, chemical shift standard: 2.50 ppm (heavy DMSO), 64 times integration, chemical shift: metaphenylenediamine (7.56 ppm), 3,5-diaminobenzoic acid (7.75 ppm), methyl 3,5-diaminobenzoate (7.78 ppm), trimesic acid chloride (8.60 ppm), isophthalic acid chloride (8.40 ppm)). The segment amount (mol %) was calculated from the peak derived from each segment component.
An amine aqueous solution containing 2.4% by weight of m-phenylenediamine (MPD), 0.9% by weight of 3,5-diaminobenzoic acid (DABA), 0.15% by weight of sodium dodecylsulfate, 2.15% by weight of triethylamine, 0.31% by weight of sodium hydroxide, 6% by weight of camphorsulfonic acid, and 1% by weight of isopropyl alcohol was applied onto a porous polysulfone support, and then an excess amine aqueous solution was removed to form an aqueous coating layer. The content ratio of MPD and DABA in the amine aqueous solution is about 80 mol % MPD and about 20 mol % DABA. Next, a surface of the aqueous coating layer was immersed in an acid chloride solution containing 0.075% by weight of trimesic acid chloride (TMC) and 0.113% by weight of isophthalic acid chloride (IPC) dissolved in a naphthenic solvent (Exxsol D40, manufactured by Exxon Mobil Corporation) for 7 seconds. Thereafter, an excess solution on the surface of the aqueous coating layer was removed, and the coating layer was air-dried for 20 seconds and further kept in a hot air dryer at 140° C. for 3 minutes to form a skin layer containing a polyamide-based resin on the porous polysulfone support, thereby forming a composite semipermeable membrane.
A composite semipermeable membrane was prepared in the same manner as in Example 1, except that an amine aqueous solution containing 2.1% by weight of m-phenylenediamine (MPD), 1.3% by weight of 3,5-diaminobenzoic acid (DABA), 0.15% by weight of sodium dodecylsulfate, 2.15% by weight of triethylamine, 0.31% by weight of sodium hydroxide, 6% by weight of camphorsulfonic acid, and 1% by weight of isopropyl alcohol was used. The content ratio of MPD and DABA in the amine aqueous solution is about 70 mol % MPD and about 30 mol % DABA.
A composite semipermeable membrane was prepared in the same manner as in Example 1, except that an amine aqueous solution containing 1.5% by weight of m-phenylenediamine (MPD), 2.1% by weight of 3,5-diaminobenzoic acid (DABA), 0.15% by weight of sodium dodecylsulfate, 2.15% by weight of triethylamine, 0.31% by weight of sodium hydroxide, 6% by weight of camphorsulfonic acid, and 1% by weight of isopropyl alcohol was used. The content ratio of MPD and DABA in the amine aqueous solution is about 50 mol % MPD and about 50 mol % DABA.
A composite semipermeable membrane was prepared in the same manner as in Example 1, except that an amine aqueous solution containing 2.7% by weight of m-phenylenediamine (MPD), 0.45% by weight of methyl 3,5-diaminobenzoate (DABAME), 0.15% by weight of sodium dodecylsulfate, 2.15% by weight of triethylamine, 0.31% by weight of sodium hydroxide, 6% by weight of camphorsulfonic acid, and 1% by weight of isopropyl alcohol was used. The content ratio of MPD and DABAME in the amine aqueous solution is about 90 mol % MPD and about 10 mol % DABAME.
A composite semipermeable membrane was prepared in the same manner as in Example 1 except that the formulation was changed to those as shown in Table 1.
| TABLE 1 | ||||
| Acid | ||||
| chloride | ||||
| solution | ||||
| Amine aqueous solution | (% by | Amount of each segment in | ||
| (% by weight) | weight) | polyamide-based resin (mol %)) | ||
| MPD | DABA | DABAME | TMC | IPC | MPD | DABA | DABAME | TMC | IPC | |
| Example 1 | 2.4 | 0.9 | — | 0.075 | 0.113 | 57.0 | 0.2 | — | 27.2 | 15.6 |
| (80 mol %) | (20 mol %) | |||||||||
| Example 2 | 2.1 | 1.3 | — | 0.075 | 0.113 | 56.3 | 0.6 | — | 27.5 | 15.5 |
| (70 mol %) | (30 mol %) | |||||||||
| Example 3 | 1.5 | 2.1 | — | 0.075 | 0.113 | 56.5 | 0.8 | — | 28.4 | 14.3 |
| (50 mol %) | (50 mol %) | |||||||||
| Example 4 | 2.7 | — | 0.45 | 0.075 | 0.113 | 55.9 | — | 3 | 25 | 16.1 |
| (90 mol %) | (10 mol %) | |||||||||
| Comparative | 3.0 | — | — | 0.075 | 0.113 | 58.1 | — | — | 25.8 | 16.1 |
| Example 1 | (100 mol %) | |||||||||
| Comparative | 0.8 | 2.6 | — | 0.075 | 0.113 | 56.1 | 1.2 | — | 28.6 | 14.1 |
| Example 2 | (30 mol %) | (70 mol %) | ||||||||
| Permeation | |||
| MPD:DABA or DABAME | flux | Rejecting rate (%) |
| (mol %) | (m3/m2 · d) | NaCl | B | IPA | |||
| Example 1 | 99.65:0.35 | 0.88 | 99.72 | 92.36 | 98.20 | ||
| Example 2 | 98.95:1.05 | 0.90 | 99.74 | 92.38 | 98.23 | ||
| Example 3 | 98.6:1.4 | 0.90 | 99.75 | 89.90 | 97.10 | ||
| Example 4 | 94.9:5.1 | 0.87 | 99.70 | 92.30 | 98.20 | ||
| Comparative | — | 0.79 | 99.68 | 92.38 | 98.20 | ||
| Example 1 | |||||||
| Comparative | 97.9:2.1 | 0.86 | 99.04 | 82.06 | 88.50 | ||
| Example 2 | |||||||
The composite semipermeable membrane and the spiral wound separation membrane element of the present invention are suitably used for production of ultrapure water, desalination of brackish water or sea water, etc., and usable for removing or collecting pollution sources or effective substances from pollution, which causes environment pollution occurrence, such as dyeing drainage and electrodeposition paint drainage, leading to contribute to closed system for drainage. Furthermore, the membrane can be used for concentration of active ingredients in foodstuffs usage, for an advanced water treatment, such as removal of harmful component in water purification and sewage usage etc. Moreover, the membrane can be used for waste water treatment in oil fields or shale gas fields.
Claims (5)
1. A composite semipermeable membrane having a skin layer containing a polyamide-based resin on a surface of a porous support,
wherein the polyamide-based resin is obtained by polymerizing a polyfunctional acid halide component and a polyfunctional amine component, and the polyfunctional amine component contains m-phenylenediamine and at least one diamine compound represented by general formula (1) below:
wherein one of R1 and R2 represents COOH, and the other represents a hydrogen atom; and each of R3 and R4 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and
a ratio (mol %) of a segment (A) derived from m-phenylenediamine and a segment (B) derived from the diamine compound in the polyamide-based resin is 99.75:0.25 to 98.5:1.5 (segment (A):segment (B)) wherein a total amount of the segment (A) and the segment (B) is 50 mol % or more when an amount of a segment derived from all polyfunctional amine components is 100 mol %.
2. The composite semipermeable membrane according to claim 1 , wherein the total amount of the segment (A) and the segment (B) is 50 to 70 mol % when an amount of a segment derived from all monomer components is 100 mol % in the polyamide-based resin.
3. A composite semipermeable membrane having a skin layer containing a polyamide-based resin on a surface of a porous support,
wherein the polyamide-based resin is obtained by polymerizing a polyfunctional acid halide component and a polyfunctional amine component, and the polyfunctional amine component contains m-phenylenediamine and at least one diamine compound represented by general formula (2) below:
wherein one of R5 and R6 represents COOR9, and the other represents a hydrogen atom; R9 represents an alkyl group having 1 to 4 carbon atoms, and each of R7 and R8 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and
a ratio (mol % of a segment (A) derived from m-phenylenediamine and a segment (C) derived from the diamine compound in the polyamide-based resin is 97:3 to 83:17 (segment (A):segment (C)) wherein a total amount of the segment (A) and the segment (C) is 50 mol % or more when an amount of a segment derived from all polyfunctional amine components is 100 mol %.
4. The composite semipermeable membrane according to claim 3 , wherein the total amount of the segment (A) and the segment (C) is 50 to 70 mol % when an amount of a segment derived from all monomer components is 100 mol % in the polyamide-based resin.
5. A spiral wound separation membrane element comprising the composite semipermeable membrane according to claim 1 .
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-212336 | 2016-10-28 | ||
| JPJP2016-212336 | 2016-10-28 | ||
| JP2016212336A JP6774841B2 (en) | 2016-10-28 | 2016-10-28 | Composite semipermeable membrane and spiral separation membrane element |
| PCT/JP2017/038486 WO2018079589A1 (en) | 2016-10-28 | 2017-10-25 | Composite semipermeable membrane and spiral separation membrane element |
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| CA3092580A1 (en) | 2018-03-30 | 2019-10-03 | Suntory Holdings Limited | Sweetening composition inducing sweetness response through molecule other than sweet taste receptor (t1r2/t1r3) |
| JP6767562B1 (en) * | 2019-12-27 | 2020-10-14 | 日東電工株式会社 | Composite semipermeable membrane |
| JP7173406B1 (en) * | 2021-04-22 | 2022-11-16 | 東レ株式会社 | composite semipermeable membrane |
| WO2022225062A1 (en) * | 2021-04-22 | 2022-10-27 | 東レ株式会社 | Composite semipermeable membrane |
| KR20230151041A (en) * | 2021-04-22 | 2023-10-31 | 도레이 카부시키가이샤 | composite semipermeable membrane |
| CN115318113B (en) * | 2022-08-03 | 2023-10-31 | 清华大学 | Nanofiltration membrane and preparation method and application thereof |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20190068619A (en) | 2019-06-18 |
| CN109789378A (en) | 2019-05-21 |
| CN109789378B (en) | 2022-02-25 |
| JP6774841B2 (en) | 2020-10-28 |
| WO2018079589A1 (en) | 2018-05-03 |
| US20200061548A1 (en) | 2020-02-27 |
| JP2018069160A (en) | 2018-05-10 |
| KR102451858B1 (en) | 2022-10-07 |
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